CN103418435B - Hyperbranched nickel-based olefin polymerization catalyst - Google Patents
Hyperbranched nickel-based olefin polymerization catalyst Download PDFInfo
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- CN103418435B CN103418435B CN201310369112.XA CN201310369112A CN103418435B CN 103418435 B CN103418435 B CN 103418435B CN 201310369112 A CN201310369112 A CN 201310369112A CN 103418435 B CN103418435 B CN 103418435B
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Abstract
The present invention relates to a kind of hyperbranched nickel olefin polymerizing catalyst, the structural formula of hyperbranched nickel olefin polymerizing catalyst is
Wherein CnH2n+1 is saturated alkyl chain (n ≥4),R1,R2 is respectively identical or different,Independently selected from H,Methyl,One of sec-butyl or tert-butyl,The preparation method is that: it is raw material by the 1.0 generation super branched molecules and salicylide of core of fatty amine,Using anhydrous low mass molecule alcohol as solvent,Schiff base reaction is carried out,1.0 generations hyperbranched Schiff base ligand is made; Then 1.0 generations hyperbranched Schiff base ligand and Dehydrated nickel chloride are subjected to complex reaction,Hyperbranched nickel olefin polymerizing catalyst crude product is made,Crude product is repeatedly washed through low molecule monohydric alcohol,Obtain final products. Hyperbranched nickel catalyst of the present invention has the design feature of super branched molecule and nickel catalyst, can be used for vinyl polymerization and prepares higher olefins, and the catalyst synthesis processes are simple, yield is higher.
Description
Technical field
The invention belongs to organic chemical synthesis and macromolecular material crossing domain, relate more specifically to a kind of hyperbranched nickel olefin polymerizing catalyst.
Background technology
Super branched molecule is irregular three-dimensional torispherical structure, and comprise partial linear structural unit in molecule, functional moieties is positioned at molecular surface, and part is present in intramolecule.The molecular weight distribution of hyperbranched polymer is wider, has good solubility, less solution and melt viscosity.This base polymer has a large amount of functional end-group and a large amount of molecule internal cavities etc., structure unique so just, make it have the molecular motion being different from line polymer, show the property that many line polymers do not have, its building-up process is also very simple.The hyperbranched polymer of different structure is in the aspect developing application such as pharmaceutical carrier, processing modified, linking agent, coating and nano material, and therefore hyperbranched polymer causes the extensive concern of polymer science circle.
Have above-mentioned good characteristic and property of many uses just because of super branched molecule, people have carried out large quantifier elimination to it, to try hard to expand its range of application.
The people such as Qu Hongjie (Qu Hongjie. the synthesis of " broom " type molecule and demulsification performance research [D]. Daqing Petroleum Institute Master degree candidate academic dissertation, 2009.) take super branched molecule as raw material, synthesized a series of hyperbranched poly ether surface active agent with following formula (a) structure.
（a）
The people such as Guo Yandong (Guo Yandong. synthesis and characteries research [D] of broom type phenolic antioxidant. Daqing Petroleum Institute Master degree candidate academic dissertation, 2010.) take super branched molecule as raw material, synthesized the phenolic antioxidant with following formula (b) structure:
(b)
The people such as Malgas (SMITH G, CHEN R, MAPOLIE S. The synthesis and catalytic activity of a first-generation poly (propylene imine) pyridylimine palladium metallodendrimer [J]. Journal of Organometallic Chemistry, 2003, 673 (1-2): 111-115.) adopt dendritic macromole and salicylic aldehyde (or its substituent) to carry out the dendritic salicylaldimine ligand of schiff base reaction spanning tree, complex reaction is carried out again with the compound of nickel, synthesize the olefin polymerization catalysis of following formula (c) structure:
(c)
The people such as Zhao Chunbin (Zhao Chunbin, Yuan's buckwheat dragon, Huang Baotong, Deng. poly-(amide-amine) dendrimer supported titanium catalyzed ethylene polymerization [J]. polymer journal, 2007,9:810-815.) with dendritic macromole and salicylic aldehyde, nickel acetate for raw material, synthesized the catalyst for ethylene polymerization of following formula (d) structure by two-step reaction, by showing the result of study of its catalytic performance, this catalyzer has higher catalytic activity.
(d)
The people such as Smith (SMITH G, MAPOLIE S.F, Iminopyridyl-palladium dendritic catalyst precursors:evaluation in Heck reactions [J] .Journal of Molecular Catalysis A:Chemical 213 (2004) 187 – 192) react with dendritic macromole and pyridine dicarbaldehyde, Palladous chloride, synthesize the olefin polymerization catalysis of following formula (e) structure:
(e)
Shown by research, this catalytic agent has higher catalytic activity.
These above-mentioned documents are for raw material with dendritic macromole and super branched molecule or derivatives thereof, utilize dendritic macromole or the special structure of super branched molecule, by common are machine building-up reactions, tensio-active agent, oxidation inhibitor and the catalyzer with certain using value are synthesized.
Meanwhile, along with day by day widening of super branched molecule Application Areas, still have for obtaining hyperbranched compound that is novel, that have excellent properties the demand needed badly, this is also an important topic and emphasis that current super branched molecule gos deep into materialogy research.
Summary of the invention
Technical problem solved by the invention is: provide a kind of hyperbranched nickel olefin polymerizing catalyst, in preparation process, super branched molecule, salicylic aldehyde (or its substituent), nickelous chloride is adopted to be raw material, carry out two step building-up reactionss and obtain described hyperbranched nickel olefin polymerizing catalyst, the structural formula of hyperbranched nickel olefin polymerizing catalyst is
Wherein C
nh
2n+1for saturated alkyl chain, n>=4, R
1, R
2identical or different separately, independently selected from the one in H, methyl, sec-butyl or the tertiary butyl; This catalyzer can be used for the high-carbon alpha-olefin of ethylene oligomerization synthesis market in urgent need.
First super branched molecule and salicylic aldehyde (or its substituent) are carried out schiff base reaction and obtain hyperbranched Schiff base ligand, then part and nickelous chloride carried out reacting and obtain, wherein n, R
1, R
2, definition as mentioned above, its reaction formula is as follows:
A kind of preparation method of hyperbranched nickel olefin polymerizing catalyst comprises the steps:
(1) by with aliphatic amide be core 1.0 generation super branched molecule be dissolved in methyl alcohol or ethanol, under condition of nitrogen gas, add 3 g anhydrous sodium sulphate in above-mentioned solution, slowly drip salicylic aldehyde, under airtight condition of nitrogen gas, isothermal reaction certain hour, obtains mixture;
(2) reaction mixture in step (1) is cooled to 0 DEG C, negative pressure filtration, after filtrate being placed in standing 36 h of-5 DEG C of refrigerators, filter, solid organic solvent A is washed, and obtains yellow crystals, this solid is dry at 65 DEG C, obtains hyperbranched Schiff base ligand;
(3) hyperbranched Schiff base ligand step (2) obtained and anhydrous methanol are inserted in vacuum reactor, under protection of inert gas, be stirred to and dissolve completely, then dropwise add the absolute methanol solution of nickelous chloride, isothermal reaction certain hour, obtains mixture;
(4) mixture step (3) obtained is at 0 DEG C of cooling certain hour, negative pressure filtration, solid organic solvent B repeatedly wash, obtain dark red solid, this solid is dried to constant weight under certain temperature, vacuum condition, obtains hyperbranched nickel olefin polymerizing catalyst.
Its preparation method: with aliphatic amide be core 1.0 generation super branched molecule and salicylic aldehyde be raw material, with anhydrous low mass molecule alcohol for solvent, carry out schiff base reaction, obtained 1.0 generation hyperbranched Schiff base ligand; Then by 1.0 generation hyperbranched Schiff base ligand and Dehydrated nickel chloride carry out complex reaction, the obtained thick product of hyperbranched nickel olefin polymerizing catalyst, thick product repeatedly washs through low molecule monohydroxy-alcohol, obtains the finished product.
In order to describe preparation method of the present invention in more detail, as follows the feature in each step and/or key element are described.
Described in step (1) take aliphatic amide as the mol ratio of core 1.0 generation super branched molecule and salicylic aldehyde two kinds of raw materials is 1:(1-5), temperature of reaction is 35-78 DEG C, and the reaction times is 8-12 h, and reaction solvent is methyl alcohol, ethanol.
Described washing organic solvent A in step (2) is the mixture of a kind of in methyl alcohol, ethanol or two kinds.
Hyperbranched Schiff base ligand described in step (3) and nickelous chloride are according to mol ratio 1:(1-1.5) react, rare gas element is nitrogen, argon gas, helium.
Temperature of reaction described in step (3) is 10-40 DEG C, the reaction times is 12-48h.
Washing organic solvent B described in step (4) is one or several mixture of methyl alcohol, ethanol, propyl alcohol, butanols.
Cooling time described in step (4) is 2h-12h, and vacuum-drying temperature is 20-70 DEG C.
Hyperbranched nickel olefin polymerizing catalyst of the present invention has excellent catalytic activity, and its preparation method is gentle, reactions steps is simple.Described hyperbranched nickel olefin polymerizing catalyst of the present invention can be used as olefin polymerization catalysis, and products distribution is higher olefins, and industrial application has good prospect.
Accompanying drawing explanation
Fig. 1 is the building-up reactions equation of hyperbranched Schiff base ligand;
Fig. 2 is the infrared spectra schematic diagram of hyperbranched Schiff base ligand in embodiment 1,2;
Fig. 3 is the building-up reactions equation of hyperbranched nickel olefin polymerizing catalyst in embodiment 3,4 and 5;
Fig. 4 is the infrared spectra schematic diagram of hyperbranched nickel olefin polymerizing catalyst in embodiment 3,4 and 5;
Fig. 5 be in embodiment 3 catalyst activity with the variation relation curve of temperature of reaction;
Fig. 6 be in embodiment 4 catalyst activity with the variation relation curve in reaction times;
Fig. 7 be in embodiment 5 catalyst activity with the variation relation curve of catalyst reaction consumption.
Embodiment
Below by specific embodiment, the present invention is described in detail:
embodiment 1
Add in the reactor that water trap is housed 3.66g with octylame be core 1.0 generation super branched molecule, 3g anhydrous sodium sulphate, adds 35ml dissolve with methanol, N
2under condition, stir, slowly drip 2.3ml salicylic aldehyde, dropwise, back flow reaction 12h at 65 DEG C.After reaction terminates, filtered while hot, after filtrate being placed in-5 DEG C of cooling 36h, filter, gained solid, at 65 DEG C of vacuum-drying 5h, obtains hyperbranched Schiff base ligand, and yield is 66.7%, and its reaction equation is as Fig. 1.The infrared spectra of hyperbranched Schiff base ligand is shown in Fig. 2.Be 1635cm in wave number
-1having there is the charateristic avsorption band of-C=N-in place, is 3412cm in wave number
-1locate the charateristic avsorption band of-OH on phenyl ring on side chain, be about 2950cm in wave number
-1and 2821cm
-1there is-CH in place
2-charateristic avsorption band, wave number is about 1497cm
-1place is the charateristic avsorption band of phenyl ring.
embodiment 2
In vacuum reactor, add 3.66g super branched molecule (n=8), 3g anhydrous sodium sulphate, add 35ml dissolve with methanol, pass into N
2stir, slowly drip 3ml salicylic aldehyde, dropwise, at 65 DEG C, back flow reaction 8h obtains.After reaction terminates, filtered while hot, after filtrate being placed in-5 DEG C of cooling 36h, filter, gained solid, at 65 DEG C of vacuum-drying 5h, obtains hyperbranched Schiff base ligand, and yield is 52.2%, and its reaction equation is as Fig. 1.The infrared spectra of hyperbranched Schiff base ligand is shown in Fig. 2.(with embodiment 1)
embodiment 3
Add the hyperbranched Schiff base ligand of 0.445 g and 5ml methyl alcohol in the reactor, 25 DEG C, N
2under condition, stir and hyperbranched Schiff base ligand is dissolved completely, slowly drip the 30.117g methanol solution that nickelous chloride massfraction is 0.39%, 25 DEG C, N
2isothermal reaction 24h under condition, the mixture negative pressure filtration obtained, solids with methanol washs three times, obtains red brown solid; By this solid 65 DEG C, be dried to constant weight under vacuum condition, obtain red brown solid powder, yield is 67%.Reaction equation is shown in Fig. 3, and its infrared absorption spectrum is shown in Fig. 4.After part and metal-complexing
v oHat 3400cm
-1neighbouring absorption peak weakens.Due to the coordination between metal and nitrogen-atoms, weaken the intensity of C=N double bond, strengthen the c h bond flexural vibration of carbon atom, thus make V
c=Nabsorption peak moves to low ripple, and therefore after coordination, the absorption peak of C=N is reduced to 1624cm
-1.Meanwhile, in part and title complex at 3250 cm
-1, 3300cm
-1all there is the N-H key stretching vibration peak of acid amides.Because metal combination key absorption peak strength is less and be less than 800cm
-1, therefore not easily recognize.
Under aluminium nickel ratio is the polymeric reaction condition of 500,30min, 0.5Mpa, be raw material with ethene, investigated the impact of temperature of reaction on catalyst activity, its activity is shown in Fig. 5 with the variation relation curve of temperature of reaction.
embodiment 4
Add in the hyperbranched Schiff base ligand of 0.445 g and 5ml methyl alcohol in the reactor, 25 DEG C, N
2under condition, stir and hyperbranched Schiff base ligand is dissolved completely, slowly drip the 30.117g methanol solution that nickelous chloride massfraction is 0.39%, 10 DEG C, N
2isothermal reaction 36h under condition, the mixture negative pressure filtration obtained, solid washing with alcohol three times, obtain red brown solid, yield is 58.7%; By this solid 50 DEG C, be dried to constant weight under vacuum condition, obtain red brown solid powder, reaction equation is shown in Fig. 3, and its infrared absorption spectrum is shown in Fig. 4.(with embodiment 3).
Aluminium nickel than be 500,25 DEG C, under the polymeric reaction condition of 0.5Mpa, be raw material with ethene, investigated the impact of reaction times on catalyst activity, its activity is shown in Fig. 6 (with embodiment 1) with the variation relation curve in reaction times.
embodiment 5
Add in the hyperbranched Schiff base ligand of 0.445 g and 5ml methyl alcohol in the reactor, 25 DEG C, N
2under condition, stir and hyperbranched Schiff base ligand is dissolved completely, slowly drip the 30.117g methanol solution that nickelous chloride massfraction is 0.73%, 10 DEG C, N
2isothermal reaction 36h under condition, the mixture negative pressure filtration obtained, solid washing with alcohol three times, obtain red brown solid, by this solid 50 DEG C, be dried to constant weight under vacuum condition, obtain red brown solid powder, yield is 52.9%, reaction equation is shown in Fig. 3, and its infrared absorption spectrum is shown in Fig. 4.(with embodiment 3) its infrared absorption spectrum is shown in Fig. 5.
At 25 DEG C, under the polymeric reaction condition of 0.5Mpa, 30min, be raw material with ethene, investigated the impact of promotor consumption on catalyst activity, its activity is shown in Fig. 7 with the variation relation curve in reaction times.
Claims (8)
1. a hyperbranched nickel olefin polymerizing catalyst, is characterized in that: the structural formula of hyperbranched nickel olefin polymerizing catalyst is
Wherein C
nh
2n+1for saturated alkyl chain, n>=4, R
1, R
2identical or different separately, independently selected from the one in H, methyl, sec-butyl or the tertiary butyl; The preparation method of hyperbranched nickel olefin polymerizing catalyst, comprises the steps:
(1) by with aliphatic amide be core 1.0 generation super branched molecule be dissolved in methyl alcohol or ethanol, under condition of nitrogen gas, add 3 g anhydrous sodium sulphate in above-mentioned solution, slowly drip salicylic aldehyde, under airtight condition of nitrogen gas, isothermal reaction certain hour, obtains mixture;
(2) reaction mixture in step (1) is cooled to 0 DEG C, negative pressure filtration, after filtrate being placed in standing 36 h of-5 DEG C of refrigerators, filter, solid organic solvent A is washed, and obtains yellow crystals, this solid is dry at 65 DEG C, obtains hyperbranched Schiff base ligand;
(3) hyperbranched Schiff base ligand step (2) obtained and anhydrous methanol are inserted in vacuum reactor, under protection of inert gas, be stirred to and dissolve completely, then dropwise add the absolute methanol solution of nickelous chloride, isothermal reaction certain hour, obtains mixture;
(4) mixture step (3) obtained is at 0 DEG C of cooling certain hour, negative pressure filtration, gained solid organic solvent B is repeatedly washed, and obtains dark red solid, this solid is dried to constant weight under certain temperature, vacuum condition, obtains hyperbranched nickel olefin polymerizing catalyst.
2. the preparation method of hyperbranched nickel olefin polymerizing catalyst as claimed in claim 1, comprises the steps:
(1) by with aliphatic amide be core 1.0 generation super branched molecule be dissolved in methyl alcohol or ethanol, under condition of nitrogen gas, add 3 g anhydrous sodium sulphate in above-mentioned solution, slowly drip salicylic aldehyde, under airtight condition of nitrogen gas, isothermal reaction certain hour, obtains mixture;
(2) reaction mixture in step (1) is cooled to 0 DEG C, negative pressure filtration, after filtrate being placed in standing 36 h of-5 DEG C of refrigerators, filter, solid organic solvent A is washed, and obtains yellow crystals, this solid is dry at 65 DEG C, obtains hyperbranched Schiff base ligand;
(3) hyperbranched Schiff base ligand step (2) obtained and anhydrous methanol are inserted in vacuum reactor, under protection of inert gas, be stirred to and dissolve completely, then dropwise add the absolute methanol solution of nickelous chloride, isothermal reaction certain hour, obtains mixture;
(4) mixture step (3) obtained is at 0 DEG C of cooling certain hour, negative pressure filtration, gained solid organic solvent B is repeatedly washed, and obtains dark red solid, this solid is dried to constant weight under certain temperature, vacuum condition, obtains hyperbranched nickel olefin polymerizing catalyst.
3. the preparation method of hyperbranched nickel olefin polymerizing catalyst as claimed in claim 2, it is characterized in that: described in step (1) take aliphatic amide as the mol ratio of core 1.0 generation super branched molecule and salicylic aldehyde two kinds of raw materials is 1:(1-5), temperature of reaction is 35-78 DEG C, and the reaction times is 8-12 h.
4. the preparation method of hyperbranched nickel olefin polymerizing catalyst as claimed in claim 2, it is characterized in that: described in step (1) take aliphatic amide as the mol ratio of core 1.0 generation super branched molecule and salicylic aldehyde two kinds of raw materials is 1:(1-5), temperature of reaction is 35-78 DEG C, and the reaction times is 8-12 h.
5. the preparation method of hyperbranched nickel olefin polymerizing catalyst as claimed in claim 2, it is characterized in that: the hyperbranched Schiff base ligand described in step (3) and nickelous chloride are according to mol ratio 1:(1-1.5) react, rare gas element is nitrogen, argon gas, helium.
6. the preparation method of hyperbranched nickel olefin polymerizing catalyst as claimed in claim 2, is characterized in that: the temperature of reaction described in step (3) is 10-40 DEG C, the reaction times is 12-48 h.
7. the preparation method of hyperbranched nickel olefin polymerizing catalyst as claimed in claim 2, is characterized in that: washing organic solvent B described in step (4) is one or several mixture of methyl alcohol, ethanol, propyl alcohol, butanols.
8. the preparation method of hyperbranched nickel olefin polymerizing catalyst as claimed in claim 2, is characterized in that: cooling time described in step (4) is 2 h-12 h, and vacuum-drying temperature is 20-70 DEG C.
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| CN110013877B (en) * | 2019-03-01 | 2020-03-10 | 东北石油大学 | Schiff base ligand covalent grafting carbon nanotube loaded late transition metal olefin polymerization catalyst and preparation method thereof |
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| AU7507001A (en) * | 2000-05-31 | 2001-12-11 | Du Pont | Catalysts for olefin polymerization |
| CN102180910B (en) * | 2011-03-11 | 2014-03-12 | 中国科学院化学研究所 | Asymmetrical alpha-diimine nickel complex catalyst and preparation method and application thereof |
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